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d10s2 post-transition metal anions: identifying and analyzing their dual-mode Lewis basicity

Seymour, J. M., Gousseva, E., Parker, L. G. ORCID: https://orcid.org/0000-0001-8727-4116, Towers Tompkins, F. K., Fogarty, R. M., Frankemoelle, L., Rowe, R. ORCID: https://orcid.org/0000-0003-3074-2040, Clarke, C. J. ORCID: https://orcid.org/0000-0003-2698-3490, Duncan, D. A. ORCID: https://orcid.org/0000-0002-0827-2022, Palgrave, R. G. ORCID: https://orcid.org/0000-0003-4522-2486, Bennett, R. A. ORCID: https://orcid.org/0000-0001-6266-3510, Hunt, P. A. ORCID: https://orcid.org/0000-0001-9144-1853 and Lovelock, K. R. J. ORCID: https://orcid.org/0000-0003-1431-269X (2025) d10s2 post-transition metal anions: identifying and analyzing their dual-mode Lewis basicity. Journal of Physical Chemistry Letters. ISSN 1948-7185

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To link to this item DOI: 10.1021/acs.jpclett.4c03649

Abstract/Summary

Liquid-phase d10s2 post-transition metal anions, such as [SnCl3]−, appear in a range of applications with a focus on catalysis and material preparation. However, little is known about their electronic structure and how it relates to reactivity. Using X-ray photoelectron spectroscopy and ab initio calculations, we demonstrate that liquid-phase d10s2 post-transition metal anions can act as dual-mode Lewis bases, interacting through the metal center and/or the ligands, with the interaction mode depending on the identity of the Lewis acid/electron acceptor. The Lewis basicity of the metal donor atom is controlled mainly by the metal identity; the ligand can be used for fine-tuning. Changing the metal center has a strong effect on the ligand basicity. These findings provide insight into d10s2 post-transition metal anion electronic structure, which will enable better molecular-level design of catalytic systems.

Item Type:Article
Refereed:Yes
Divisions:Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:121887
Publisher:American Chemical Society

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